Water-soluble cellulose ether and method for producing the same

ABSTRACT

A method for producing a highly viscous water-soluble cellulose ether has a small undissolved fiber content and a high loose bulk density. More specifically, a production method includes steps of: bringing cellulose pulp into contact with an alkali metal hydroxide solution to obtain an alkali cellulose mixture; draining the alkali cellulose mixture to obtain an alkali cellulose; reacting the alkali cellulose with an etherifying agent to obtain a water-soluble cellulose ether mixture; washing and draining the water-soluble cellulose ether mixture to obtain a first moist cellulose ether; mixing the first moist cellulose ether with water to obtain a second moist cellulose ether; coarsely pulverizing the second moist cellulose ether with a coarse pulverizer to obtain a coarsely pulverized cellulose ether; cooling the coarsely pulverized cellulose ether; and then drying and pulverizing the coarsely pulverized cellulose ether.

This application is a Divisional of application Ser. No. 16/013,088,filed Jun. 20, 2018, which claims priority to Japanese Application No.2018-109220, filed Jun. 7, 2018, and Japanese Application No.2017-131736, filed Jul. 5, 2017. The entire contents of the priorapplications are incorporated by reference herein in their entirety.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The invention relates to a water-soluble cellulose ether used in thefields of construction materials, chemicals, pharmaceuticals, food andothers, and to a method for producing the water-soluble cellulose ether.

2. Related Art

The crystallinity of a cellulose is considered to greatly depend on theintramolecular hydrogen bonds between hydroxy groups constituting theskeletal structure of the cellulose molecule. The hydrogen bond is sostrong as to interfere with hydration with water molecules in water, andthus the cellulose is water-insoluble. Hence, a water-soluble celluloseether is produced by treating a cellulose with an alkali metal hydroxidesolution such as an aqueous sodium hydroxide solution to obtain alkalicellulose having the crystal structure of the cellulose destroyed, andthen reacting the alkali cellulose with an etherifying agent to obtain awater-soluble cellulose ether as a result of substitution of the hydroxygroups of the cellulose.

Conventionally, water-soluble cellulose ethers have been used forpharmaceutical products, binders for foods, thickeners for varioussolvents, and binders for extrusion molding and ceramic-formingmaterials. Unless a water-soluble cellulose ether is dissolved at amolecular level to provide a transparent aqueous solution, a product mayhave a defective portion or have a poor function. A water-solublecellulose ether to be used as a various binder or thickener ispreferably a cellulose ether capable of providing a highly viscousaqueous solution. However, the water-soluble cellulose ether capable ofproviding high viscosity yields the larger number of undissolved fibersthan a water-soluble cellulose ether which provides low viscosity, andis considered to be difficult to obtain a transparent aqueous solution.

Moreover, the water-soluble cellulose ether capable of providing highviscosity is likely to have a lower loose bulk density than awater-soluble cellulose ether which provides low viscosity. In general,a cellulose ether powder having a low loose bulk density contains suchcellulose ether fibers as to reduce the flowability at a high content,thereby deteriorating the powder flowability. When a powder has poorflowability, for example, the powder fed from a hopper is apt to causetroubles such as powder bridging.

There is a method for producing a water-soluble cellulose ether capableof providing a highly viscous aqueous solution with a low undissolvedfiber content, comprising steps of: bringing pulp having a particularpore volume into contact with an alkali metal hydroxide solution toobtain an alkali cellulose mixture, wherein the pulp is in form of asheet or chips into which the sheet is converted; draining an excessalkali metal hydroxide solution from the alkali cellulose mixture tocollect alkali cellulose; and reacting the alkali cellulose with anetherifying agent to obtain a water-soluble cellulose ether. The methodexcels in uniformity of alkali distribution in the alkali cellulose incomparison with a method comprising a step of bringing powder pulp intocontact with an alkali metal hydroxide solution, thereby lowering thenumber of undissolved fibers (JP 2009-173907A).

There is another method of reducing the number of water-insoluble fibersin a water-soluble cellulose derivative, comprising steps of: addingwater of 50° C. or higher to a water-soluble cellulose derivative toobtain a mixture having a water content of 35 to 90% by mass; and dryingand pulverizing the mixture, while keeping the mixture at a temperatureof not less than 50° C. (JP 2014-510183T, which is a Japanese phasepublication of WO 2012/138531.).

There is a method of producing a water-soluble cellulose ether from awater-soluble cellulose capable of providing high viscosity comprisingsteps of: mixing a moist cellulose ether with water to obtain acellulose-ether-feeding composition having a water content of 50 to 80%by mass; and pulverizing the composition in a high-speed impact millwhile heating (JP 2001-240601A).

SUMMARY OF THE INVENTION

There is a room for improvement in a loose bulk density of thewater-soluble cellulose ether capable of providing the high viscosityproduced by the method described in JP 2009-173907A. It is because thereare cases where the water-soluble cellulose ether in form of powdercontains flowability-lowering cellulose ether fibers at a high content.

As for the cellulose ether capable of providing the high viscosityproduced by the method described in JP 2014-510183T, water brought intocontact with a water-soluble cellulose derivative has a high temperatureso that the fibrous form of cellulose ether is unlikely to disappear andremains. Although the produced water-soluble cellulose ether containsflowability-lowering cellulose ether fibers at a small content ascompared with that in JP 2009-173907A, it cannot have a satisfactoryloose bulk density.

In the production method described in JP 2001-240601A, when a moistcellulose ether is mixed with water, only the surface of the celluloseether lump is dissolved to form a highly viscous gelatinous film on thesurface. Thus, water does not reach the inside of the lump so that wateris non-uniformly distributed. Consequently, a portion in which thefibrous form of the cellulose ether does not disappear is left as afibrous cellulose ether, thereby deteriorating the loose bulk density.

In the presence of these problems, there is a demand for a water-solublecellulose ether, being capable of providing the high viscosity andhaving a small undissolved fiber content and a high loose bulk density;and a method for producing the water-soluble cellulose ether.

As a result of intensive studies for achieving the object, the inventorshave found that a water-soluble cellulose ether, being capable ofproviding the high viscosity and having the decreased number ofundissolved fibers and a high loose bulk density, can be produced by amethod for producing the water-soluble cellulose comprising steps of:adjusting the water content of the washed water-soluble cellulose etherproduct, and coarsely pulverizing the product; and have completed theinvention.

In an aspect of the invention, there is provided a method for producinga water-soluble cellulose ether, comprising steps of: bringing cellulosepulp into contact with an alkali metal hydroxide solution to obtain analkali cellulose mixture; draining the alkali cellulose mixture tocollect alkali cellulose; reacting the alkali cellulose with anetherifying agent to obtain a water-soluble cellulose ether mixture;washing and draining the water-soluble cellulose ether mixture tocollect a first moist cellulose ether; mixing the first moist celluloseether with water to obtain a second moist cellulose ether; coarselypulverizing the second moist cellulose ether to obtain a coarselypulverized cellulose ether; cooling the coarsely pulverized celluloseether; and then drying and pulverizing the coarsely pulverized celluloseether to obtain a water-soluble cellulose ether.

In another aspect of the invention, there is provided a water-solublecellulose ether, having a loose bulk density of 0.36 to 0.60 g/ml;having a viscosity at 20° C. of 30,000 to 500,000 mPa·s as determined ina 2% by mass aqueous solution of the water-soluble cellulose ether; andcontaining 800 or less undissolved fibers, each fiber having a dimensionof 8 to 200 μm, as determined by a Coulter counter method at 25° C. in 2ml of a 0.1% by mass aqueous solution of the water-soluble celluloseether.

According to the invention, a water-soluble cellulose ether, beingcapable of providing the high viscosity and having a high loose bulkdensity and the decreased number of undissolved fibers, can beefficiently produced. For example, a water-soluble cellulose etherhaving a loose bulk density of 0.36 to 0.60 g/ml, having a viscosity at20° C. of 30,000 to 500,000 mPa·s as determined in a 2% by mass aqueoussolution of the water-soluble cellulose ether, and containing 800 orless of undissolved fibers, each fiber having a dimension of 8 to 200μm, as determined by a Coulter counter method at 25° C. in 2 mL of a0.1% by mass aqueous solution of the water-soluble cellulose ether, canbe produced.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention will now be described in further detail.

First, a step of bringing cellulose pulp into contact with an alkalimetal hydroxide solution to obtain an alkali cellulose mixture will bedescribed.

Examples of the raw material of the cellulose pulp include wood pulp andcotton linter pulp. The wood pulp is preferable from the viewpoint ofreducing the number of undissolved fibers. Examples of tree species forthe wood pulp may include conifers such as pines, spruces and Tsugasieboldii, and broadleaf trees such as eucalyptuses and maples. The pineis preferable from the viewpoint of reducing the number of undissolvedfibers.

The intrinsic viscosity of the cellulose pulp, which is an index of thepolymerization degree of the cellulose pulp, is preferably 1,300 to3,000 ml/g, more preferably 1,400 to 2,500 ml/g, as determined inaccordance with the viscosity measurement in JIS P8215 from theviewpoint of obtaining a water-soluble cellulose ether capable ofproviding the high viscosity.

The cellulose pulp is preferably in form of a sheet or chips from theviewpoint of handleability and drainability of the alkali cellulose.

The pulp sheet preferably has a thickness of 0.1 to 5.0 mm, morepreferably 0.5 to 2.0 mm from the viewpoint of handleability duringdraining.

The pulp sheet preferably has a density of 0.60 g/ml or less from theviewpoint of reducing the number of undissolved fibers. The lower limitof the density of the pulp sheet may be any value that can beindustrially achieved, and is typically 0.30 g/ml.

The pulp sheet preferably has an alpha-cellulose content of 90% by massor more from the viewpoint of suppressing the reduction in the alkaliabsorption rate and reducing the number of undissolved fibers. Thealpha-cellulose content may be determined in accordance with TEST METHODT429 of The Technical Association of Pulp and Paper Industry (TAPPI).

The pulp sheet may be used as it is, or the pulp chips into which thepulp sheet is converted may also be used.

The shape of the pulp chip is preferably a quadrangle having a sidelength of 2 to 100 mm, more preferably 3 to 50 mm from the viewpoint ofhandleability during immersion and reducing the number of undissolvedfibers. The pulp chip has substantially the same thickness as thethickness of the pulp sheet.

The pulp chips may be prepared by cutting a pulp sheet. The pulp chipsmay be prepared by any method, and a conventional cutter such as aslitter cutter may be used. A cutting apparatus enabling continuouscutting is more advantageous from the investment cost.

The alkali metal hydroxide solution may be any solution capable ofproducing alkali cellulose, and is preferably an aqueous sodiumhydroxide solution or an aqueous potassium hydroxide solution from theviewpoint of economy.

The alkali metal hydroxide solution preferably has a concentration of 23to 60% by mass, more preferably 35 to 55% by mass from the viewpoint ofimproving the efficiency of the reaction with an etherifying agent. Thealkali metal hydroxide solution is preferably an aqueous solution, ormay be an alcohol solution such as an ethanol solution or a mixedsolution of a water-soluble alcohol and water.

The temperature at which cellulose pulp is brought into contact with thealkali metal hydroxide solution is preferably 5 to 70° C., morepreferably 15 to 60° C. from the viewpoint of productivity andsuppression of uneven alkali distribution in the alkali cellulose.

The contact time between the cellulose pulp and the alkali metalhydroxide solution is preferably 10 to 600 seconds, more preferably 15to 120 seconds from the viewpoint of suppression of uneven distributionof alkali in the alkali cellulose and obtaining the alkali cellulosehaving an intended composition.

The mass ratio of the alkali metal hydroxide solution contained by thealkali cellulose mixture to the solid component in the pulp (alkalimetal hydroxide solution/solid component in pulp) is preferably 3 to5,000, more preferably 10 to 200, even more preferably 20 to 60 from theviewpoint of a facility scale and reducing the number of undissolvedfibers.

The amount of the alkali metal hydroxide solution to be used may beappropriately selected depending on the above mass ratio.

The solid component in pulp means a component excluding a watercomponent in the pulp. The solid component in pulp includes, in additionto cellulose as the main component, organic matter such ashemicelluloses, lignins and resins, and inorganic matter such as Sicomponents and Fe components. The solid component in pulp may becalculated from a dry matter content determined in accordance withPulps-Determination of dry matter content in JIS P8203: 1998. The drymatter content is determined by the method comprising steps of: drying asample at 105±2° C. until the mass reaches a constant value; anddividing the mass after drying by the mass before drying to obtain thedry matter content (unit: % by mass).

Next, a step of draining (i.e. deliquoring) the alkali cellulose mixtureto collect alkali cellulose will be described. The alkali cellulose maybe prepared by the method comprising steps of: bringing cellulose pulpinto contact with an alkali metal hydroxide solution to obtain an alkalicellulose mixture, and then draining the alkali cellulose mixture toremove an excess alkali metal hydroxide solution.

Examples of the draining method include a method comprising a steps of,after immersing a pulp sheet in an alkali metal hydroxide solutionplaced in a bath, pressing the resulting mixture with a roller or asimilar device; and a method comprising a step of, after immersing pulpchips in an alkali metal hydroxide solution placed in a bath, subjectingthe resulting mixture to centrifugation or the other mechanicalseparation.

The mass ratio of the alkali metal hydroxide component in the alkalicellulose to the solid component in the pulp (alkali metal hydroxidecomponent/solid component in pulp) is preferably 0.50 to 2.00, morepreferably 0.60 to 1.80 from the viewpoint of reducing the number ofundissolved fibers.

By appropriately selecting the pressing time or conditions in the stepof pressing, or the rotation speed of and the residence time in acentrifuge separator, alkali cellulose having an intended mass ratio ofthe alkali metal hydroxide component to the solid component in the pulp(alkali metal hydroxide component/solid component in pulp) may beprepared.

As for the draining temperature such as a temperature of pressing orcentrifugation, the alkali cellulose mixture prepared by bringingcellulose pulp into contact with an alkali metal hydroxide solution maybe drained as it is in the absence of heating or cooling.

The mass of the alkali metal hydroxide component may be determined byneutralization titration.

Next, a step of reacting the alkali cellulose with an etherifying agentto obtain a water-soluble cellulose ether mixture will be described.

The alkali cellulose may be supplied into an etherification reactor asit is or after subjected to optional cutting or disintegration. Theetherification reactor is preferably a reactor with a stirringmechanism, allowing the etherification reaction to proceed whilemechanically loosening the alkali cellulose, from the viewpoint ofreducing the number of undissolved fibers. Examples of the reactorinclude a plough type shovel blade mixer. After the alkali cellulose issupplied into a reactor, the oxygen in the reactor is preferably removedby a vacuum pump or the like and replaced with an inert gas, preferably,nitrogen gas.

In order to suppress local generation of heat in the etherificationreactor, an organic solvent inert to the etherification reaction, suchas dimethyl ether, may be added into the system after the alkalicellulose is supplied.

Examples of the etherifying agent include an alkylating agent such asmethyl chloride and ethyl chloride; and a hydroxyalkylating agent suchas ethylene oxide and propylene oxide. The etherifying agent ispreferably supplied after the alkali cellulose is supplied into areactor. The etherifying agent is added in such an amount that aresulting water-soluble cellulose ether will have an intendedsubstitution degree.

When the etherifying agent is supplied to the etherification reactor,the inside temperature of the etherification reactor is preferably 40 to90° C., more preferably 50 to 85° C. from the viewpoint of reactioncontrol. The supply time for supplying the etherifying agent ispreferably 10 to 120 minutes, more preferably 10 to 100 minutes from theviewpoint of reaction control or productivity.

After the etherifying agent is supplied, the mixing with stirring ispreferably continued in order to complete the etherification reaction.The mixing-with-stirring time after the etherifying agent is supplied ispreferably 10 to 80 minutes, more preferably 20 to 60 minutes from theviewpoint of productivity. The inside temperature of the reactor afterthe etherifying agent is supplied is preferably 70 to 120° C., morepreferably 80 to 110° C. from the viewpoint of reaction control.

When a water-soluble cellulose ether not having undergone uniformsubstitution reaction is dissolved in water, there remain manyundissolved fibers, each fiber having a dimension of 8 to 200 μm, asdetermined by a Coulter counter method at 25° C. in 2 ml of a 0.1% bymass aqueous solution of the water-soluble cellulose ether.

After the completion of the etherification reaction, the gas in theetherification reactor is discharged, and then a water-soluble celluloseether mixture is taken out of the etherification reactor.

Next, a step of washing and draining the water-soluble cellulose ethermixture to collect a first moist cellulose ether will be described.

As for the washing with a liquid (e.g. water) of more than the gelationtemperature of the water-soluble cellulose ether and draining (i.e.deliquoring), the washing and the draining may be carried out separatelyor concurrently. For example, after washing, filtration or pressing maybe carried out. Alternatively, filtration or pressing may be carriedout, while adding water for washing. The washing and draining may becarried out by using a known technique. For example, the water-solublecellulose ether mixture is dispersed in water of more than the gelationtemperature for washing, and the resulting slurry of the water-solublecellulose ether mixture is drained, followed by optional pressing.

The washing of the water-soluble cellulose ether mixture includeswashing with water of a certain temperature. The washing water to beadded to the water-soluble cellulose ether mixture preferably has atemperature of 60 to 100° C., more preferably 85 to 100° C. from theviewpoint of obtaining a water-soluble cellulose ether having a low ashcontent. The concentration of the slurry of the water-soluble celluloseether mixture is preferably 1 to 15% by mass from the viewpoint ofobtaining a water-soluble cellulose ether having a low ash content.

The temperature of the water-soluble cellulose ether mixture to bewashed is the temperature after the etherification reaction, and ispreferably 70 to 120° C., more preferably 80 to 110° C.

Examples of the device to be used for draining may include a vacuumfiltration device, a pressure filtration device, a centrifugaldehydrator, a filter press, a screw press, and a V-type disk press.Examples of the device to be used for pressing are substantially thesame as examples of the device to be used for draining.

Washing water may be successively allowed to pass through the drainedwater-soluble cellulose ether mixture after washing, as optional furtherwashing. Alternatively, the filtered or pressed water-soluble celluloseether mixture after washing may be dispersed in water as optionalfurther washing, and the resulting slurry may be drained and pressed.

The first moist cellulose ether prepared by washing and draining may bein form of a block or loosened block owing to draining. It is preferablyin form of a block from the viewpoint of preventing the draining devicefrom becoming a complicatedly shaped and functioned.

The first moist cellulose ether prepared by washing and drainingpreferably has a water content of 35 to 55% by mass, more preferably 40to 50% by mass from the viewpoint of obtaining a water-soluble celluloseether having a low ash content. The water content of the first moistcellulose ether may be determined in accordance with “Loss on DryingTest” in the Japanese Pharmacopoeia Seventeenth Edition. The watercontent may be calculated as {(mass before drying−mass afterdrying)/(mass before drying)}×100(%).

The first moist cellulose ether prepared by washing and drainingpreferably has a temperature of 60 to 100° C., more preferably 80 to 95°C. in consideration of obtaining a second moist cellulose etherdescribed later.

Next, a step of mixing the first moist cellulose ether with water toobtain a second moist cellulose ether will be described.

The method of mixing the first moist cellulose ether with water toobtain a second moist cellulose ether may be any method capable ofuniform distribution of water in the second moist cellulose ether andcapable of adjusting the temperature and the water content of the secondmoist cellulose ether to intended values. From the viewpoint of uniformdistribution of water in the second moist cellulose ether, an amount ofwater required to convert the first moist cellulose ether into thesecond moist cellulose ether having a water content in a preferablerange is preferably supplied together with the first moist celluloseether into a mixer.

The water to be mixed with the first moist cellulose ether preferablyhas a temperature of 80 to 100° C., more preferably 90 to 100° C.,regardless of a batch system or a continuous system from the viewpointof obtaining a water-soluble cellulose ether having a high loose bulkdensity and achieving satisfactory operability in the following steps.

The first moist cellulose ether to be mixed with water preferably has atemperature of 60 to 100° C., more preferably 80 to 95° C., as describedabove. When the first moist cellulose ether has a temperature of lessthan 60° C., the surface of the first moist cellulose ether is dissolvedto form a highly viscous gelatinous film on the surface. Consequently,when water is added in the step of obtaining a second moist celluloseether, the water does not reach the inside of the lump of the firstmoist cellulose ether and is unevenly distributed in the first moistcellulose ether. As a result, the water-soluble cellulose ether may havea poor loose bulk density. On the other hand, it is difficult to producea first moist cellulose ether of higher than 100° C.

The second moist cellulose ether obtained by mixing with waterpreferably has a temperature of 50 to 100° C., more preferably 70 to 95°C. from the viewpoint of obtaining uniform distribution of water in acoarsely pulverized cellulose ether and obtaining a water-solublecellulose ether having the decreased number of undissolved fibers and ahigh loose bulk density.

The second moist cellulose ether obtained by mixing the first moistcellulose ether with water preferably has a water content of 60 to 90%by mass, more preferably 60 to 85% by mass, even more preferably 65 to80% by mass from the viewpoint of obtaining a water-soluble celluloseether having a high loose bulk density.

The water content of the second moist cellulose ether obtained by mixingthe first moist cellulose ether with water may be determined inaccordance with “Loss on Drying Test” in the Japanese PharmacopoeiaSeventeenth Edition as with the water content of the first moistcellulose ether.

The system of mixing the first moist cellulose ether with water may bethe batch system or the continuous system. It is preferably thecontinuous system from the viewpoint of uniform distribution of water inthe second moist cellulose ether and industrial production.

In the case of the batch system, the first moist cellulose ether issupplied together with water into a mixer with stirring and a jacket,and is mixed with stirring to obtain a second moist cellulose ether. Aknown mixer with stirring may be used. Examples of the mixer withstirring include a ribbon mixer, a screw mixer, a rotor mixer with pins,a paddle mixer, a mixer with paddles, a proshear mixer, a twin-screwkneader, a co-kneader, a votator kneader, a self-cleaning kneader, and abiaxial kneader. As a preferred manner of adding water to the firstmoist cellulose ether in the case of the batch system, dropwise additionor spraying of water through an inlet or into the mixer with stirringmay be carried out. The dropwise addition or spraying of water may becarried out at a single position or two or more positions.

The stirring speed of a mixer with stirring to be used in the batchsystem is preferably 0.05 to 150 m/s, more preferably 0.1 to 20 m/s,even more preferably 0.2 to 10 m/s in terms of the peripheral speed of astirring propeller from the viewpoint of suppressing excess powerconsumption for stirring or evaporation of water in a stirring mixtureowing to stirring heat. The mixing-with-stirring time is preferably 1second to 60 minutes, more preferably 1 second to 30 minutes from theviewpoint of suppression of uneven distribution of water in the secondmoist cellulose ether or industrial production.

The mixer with stirring to be used in the batch system preferably has atemperature-holding or heating function from the viewpoint of preventingonly the surface of the first moist cellulose ether from dissolving toform a highly viscous gelatinous film on the surface. For example, themixer with stirring preferably comprises a cover of a heat-insulatingmaterial, or a jacket whose temperature is maintained at 80 to 100° C.

In the case of the continuous system, an amount of water required toconvert the first moist cellulose ether into the second moist celluloseether having a water content in a preferable range is preferablysupplied together with the first moist cellulose ether into a conveyormixer, thereby obtaining the second moist cellulose ether. Any knownconveyor mixer may be used. A screw conveyor mixer capable ofquantitatively supplying a first moist cellulose ether is preferable.The shape of the screw in the screw conveyor mixer is not particularlylimited. A screw with a paddle or a ribbon screw is preferable from theviewpoint of uniform distribution of water in the second moist celluloseether.

As for the running conditions of the conveyor mixer to be used in thecontinuous system, the shape, the pitch and the rotation speed of thescrew are preferably selected so that the conveyance time is preferably1 second to 60 minutes, more preferably 1 second to 30 minutes from theviewpoint of suppression of uneven distribution of water in the secondmoist cellulose ether and an appropriate size of the conveyor mixer. Thetemperature in the conveyor mixer is preferably 80 to 100° C., morepreferably 90 to 100° C. from the viewpoint of preventing only thesurface of the first moist cellulose ether from dissolving to form ahighly viscous gelatinous film on the surface.

The second moist cellulose ether may be in form of a block or a blockloosened by a shear force in a mixer.

The second moist cellulose ether in form of a loosened block has anaverage particle size of 10 to 30 mm. The average particle size is aparticle size at a value of 50% in a mass-based cumulative particle sizedistribution by a sieve method. More specifically, the sieving iscarried out in accordance with manual sieving in JIS Z 8815 (Testsieving—General requirements) using sieves having different openings:45.0 mm for sieve-1, 37.5 mm for sieve-2, 22.4 mm for sieve-3, 16.0 mmfor sieve-4, 11.2 mm for sieve-5, 8.0 mm for sieve-6, 4.0 mm forsieve-7, 2.0 mm for sieve-8, 1.0 mm for sieve-9 and 0.425 mm forsieve-10; and plotting accumulative percentages on the sieves in theRosin-Rammler chart to select the particle size at 50% as the averageparticle size. It is preferable to use at least five sieves havingdifferent openings for sieving of the second moist cellulose ether. Whenat least five sieves are selected from the above ten sieves, the sieveshaving consecutive numbers connected with hyphens, such as sieve-2 to -6or sieves-3 to -7, are preferably used from the standpoint ofreproducibility and accuracy of the measured values.

Next, a step of coarsely pulverizing the second moist cellulose ether toobtain a coarsely pulverized cellulose ether will be described.

A coarse pulverizer to be used for the coarse pulverization typicallypulverizes a material having high hardness such as rock and having aparticle size of 500 to 2,000 mm by use of strong external force into asize of about 3 to 70 mm. Dry pulverization is typically performed topulverize a dried material. Accordingly, it has been considered that amoist material having strong adhesiveness such as the second moistcellulose ether adheres to a surface of the coarse pulverizer and growsthereon, and it cannot be coarsely pulverized.

Surprisingly, the inventors have found that the coarse pulverizer isapplicable without adhesion or growth in the coarse pulverizer and issuitable for uniform distribution of water in the second moist celluloseether. It is because the coarse pulverizer does not excessivelypulverize a moist fibrous material having strong adhesiveness such asthe second moist cellulose ether, and has a short residence time in thecoarse pulverizer.

The coarse pulverizer is preferably a pulverizer, for example, whichallows a target material to be brought into direct contact with apulverizing blade attached to a rotation rotor, and to be subjected toan external force such as compression, impact and shear. By applicationof strong compression and impact to the second moist cellulose ether,the added water present mainly around the surface of the second moistcellulose ether uniformly penetrates into the inside of the second moistcellulose ether. In addition, by concurrent application of shear, theparticles of the second moist cellulose ether become finer, therebyfacilitating the movement of water from the surface to the inside of thesecond moist cellulose ether. As a result of these effects, a coarselypulverized cellulose ether having more uniform water distribution thanthat of the second moist cellulose ether can be prepared. Althoughpulverization and drying are often used in combination, this coarsepulverization is used for achieving more uniform water distribution sothat it is not combined with drying.

The temperature of the coarse pulverization varies depending on a typeof coarse pulverizer so that it may be selected appropriately inaccordance of pulverization of a coarse pulverizer to be used. It is,for example, 10 to 90° C.

The water distribution in each of the second moist cellulose ether andthe coarsely pulverized cellulose ether may be evaluated by the absolutevalue of the difference in water content between the surface part andthe center part and by the water content ratio of the surface part tothe center part.

Each water content of the surface part and the center part of the secondmoist cellulose ether or the coarsely pulverized cellulose ether isdetermined by the method comprising steps of: collecting several gramsof samples from five different positions in the surface part and fromfive different positions in the center part; and measuring and averagingthe water contents at the respective five positions.

The surface part is an area in contact with air and the vicinity of thearea in the second moist cellulose ether or the coarsely pulverizedcellulose ether, and corresponds the gathering of each position having“a ratio of the distance between the center and the position in thesurface part to the maximum direct distance between the center and thecircumference of the second moist cellulose ether or the coarselypulverized cellulose ether” of 0.75 to 1.00 in terms of each crosssection passing through the center thereof.

The center part corresponds to the gathering of such a position that aratio of (the distance between the center and the position in the centerpart) to (the maximum direct distance between the center and thecircumference of the second moist cellulose ether or the coarselypulverized cellulose ether) is 0 to 0.25 in terms of each cross sectionpassing through the center of the second moist cellulose ether or thecoarsely pulverized cellulose ether.

Regarding each of the second moist cellulose ether and the coarselypulverized cellulose ether, as the absolute value of the difference inwater content average between the surface part and the center part issmaller and as the water content ratio of the surface part to the centerpart is closer to 1.00:1.00, water penetrates more into the center sothat the distribution of water is more uniform.

The absolute value of the difference in water content between thesurface part and the center part of the coarsely pulverized celluloseether is preferably 0.0 to 2.5% by mass, more preferably 0.0 to 1.5% bymass from the viewpoint of obtaining satisfactory loose bulk density,and the water content ratio of the surface part to the center part ispreferably 1.03:1.00 to 1.00:1.00, more preferably 1.02:1.00 to1.00:1.00. Examples of the coarse pulverizer include a cone crusher, animpact crusher, a hammer mill, and a feather mill. The feather mill ispreferred from the viewpoint of suppression of the reduction in watercontent of the moist cellulose ether due to pulverization heat andsuppression of excess pulverization.

The running conditions of the coarse pulverizer vary depending on a typeof the coarse pulverizer. The rotation speed of the coarse pulverizerand the arrangement of a pulverizing blade in the coarse pulverizer areselected in such a manner that the coarsely pulverized cellulose etherwill preferably have an average particle size of 3 to 12 mm. Dependingon a type of the coarse pulverizer, an optional classification unit maybe installed in the coarse pulverizer. Examples of the pulverizing bladeinclude a knife blade, a hammer blade, and a flat blade. The knife bladeis preferred from the viewpoint of uniform distribution of water in thesecond moist cellulose ether.

The coarsely pulverized cellulose ether preferably has an averageparticle size of 3 to 12 mm, more preferably 5 to 10 mm. When thecoarsely pulverized cellulose ether has an average particle size of lessthan 3 mm, a moist cellulose ether may have a lower water content or maybe excessively pulverized. When the coarsely pulverized cellulose etherhas an average particle size of more than 12 mm, water may not penetrateinto the center part by the coarse pulverization, so that a coarselypulverized cellulose ether having a more uniform water distribution thanthat of the second moist cellulose ether may not be obtained. Theaverage particle size of the coarsely pulverized cellulose ether is aparticle size at a value of 50% in a mass-based cumulative particle sizedistribution by a sieve method. More specifically, the sieving iscarried out in accordance with manual sieving in JIS Z 8815 (Testsieving—General requirements) using sieves having different openings:45.0 mm for sieve-1, 37.5 mm for sieve-2, 22.4 mm for sieve-3, 16.0 mmfor sieve-4, 11.2 mm for sieve-5, 8.0 mm for sieve-6, 4.0 mm forsieve-7, 2.0 mm for sieve-8, 1.0 mm for sieve-9 and 0.425 mm forsieve-10; and plotting accumulative percentages on the sieves in theRosin-Rammler chart to select the particle size at 50% as the averageparticle size. It is preferable to use at least five sieves havingdifferent openings for sieving of the coarsely pulverized celluloseether. When at least five sieves are selected from the above ten sieves,the sieves having consecutive numbers connected with hyphens, such assieve-2 to -6 or sieve-3 to -7, are preferably used from the standpointof reproducibility and accuracy of the measured values.

The residence time of the second moist cellulose ether in the coarsepulverizer is preferably 0.1 seconds to 3 minutes, more preferably 0.1seconds to 2 minutes, even more preferably 0.1 seconds to 1 minute. Itis difficult to set the residence time of the second moist celluloseether in the coarse pulverizer at less than 0.1 seconds. When theresidence time is more than 3 minutes, the second moist cellulose ethermay have a lower water content du to pulverization heat, or may beexcessively pulverized.

When a kneader or the like is used to apply a shear force, it typicallytakes about 5 to 10 minutes. However, a coarse pulverize does not needsuch a time. Hence, for example, depolymerization or excesspulverization is unlikely to be caused by an excess shear force. Inparticular, the reduction in viscosity or loose bulk density, or theincrease in the number of undissolved fibers of a water-solublecellulose ether capable of providing the highly viscosity can besuppressed.

The peripheral speed of a pulverizing part which applies an externalforce to the second moist cellulose ether in the coarse pulverizer ispreferably 0.05 to 200 m/s, more preferably 0.1 to 150 m/s. When theperipheral speed is less than 0.05 m/s, the second moist cellulose ethermay not be coarsely pulverized into an intended average particle size.When the peripheral speed is more than 200 m/s, the power consumptionfor stirring may be excess, or water may evaporate during coarsepulverization so that a water-soluble cellulose ether having a highloose bulk density may not be obtained.

If an excess pulverizing energy is generated during the coarsepulverization, the pulverization energy may be converted into heat,which may heat the second moist cellulose ether. Consequently, the watertherein may evaporate so that the second moist cellulose ether may havea lower water content.

The water content reduction ratio caused by subjecting the second moistcellulose ether to the coarse pulverizer is preferably 0 to 20% by mass,more preferably 0 to 10% by mass from the viewpoint of obtaining awater-soluble cellulose ether having a high loose bulk density. Thewater content reduction ratio is defined by {100% by mass−(water contentof coarsely pulverized cellulose ether)/(water content of second moistcellulose ether)×100}.

The water content of the second moist cellulose ether to be subjected tothe coarse pulverization is preferably 60 to 90% by mass, morepreferably 60 to 85% by mass, even more preferably 65 to 80% by massfrom the viewpoint of obtaining a water-soluble cellulose ether having ahigh loose bulk density.

The water content of the second moist cellulose ether to be subjected tothe coarse pulverization may be determined in accordance with “Loss onDrying Test” in the Japanese Pharmacopoeia Seventeenth Edition as withthe water content of the first moist cellulose ether.

The temperature of the second moist cellulose ether to be subjected tothe coarse pulverization is preferably 50 to 100° C., more preferably 70to 95° C. from the viewpoint of uniform distribution of the water in thecoarsely pulverized cellulose ether and obtaining a water-solublecellulose ether having the decreased number of undissolved fibers andhaving a high loose bulk density.

Next, a step of cooling the coarsely pulverized cellulose ether, andthen a step of drying and pulverizing the coarsely pulverized celluloseether to obtain a water-soluble cellulose ether will be described.

The coarsely pulverized cellulose ether is cooled to preferably in arange of from 0 to 40° C., more preferably in a range of from 5 to 30°C., even more preferably in a range of from 5 to 20° C. from theviewpoint of obtaining a water-soluble cellulose ether having a highloose bulk density. To cool the coarsely pulverized cellulose ether, aknown cooling method may be used. Examples of the cooling method includea method of bringing the coarsely pulverized cellulose ether intocontact with a cooled heat-transfer surface, a method of bringing thecoarsely pulverized cellulose ether into contact with cold air, and amethod of utilizing vaporization heat. A cooling device used in thecooling method is applicable to either a batch system or a continuoussystem.

By cooling, the coarsely pulverized cellulose ether loses the fibershape thereof so that a water-soluble cellulose ether having a highloose bulk density can be produced.

When the coarsely pulverized cellulose ether is cooled by the method ofbringing a coarsely pulverized cellulose ether into contact with acooled heat-transfer surface, a device with a jacket is preferably usedfor cooling. The jacket temperature is preferably 40° C. or less, morepreferably −40 to 30° C. When the jacket temperature is more than 40°C., a water-soluble cellulose ether having a high loose bulk density maynot be produced.

The residence time in the cooling device in the method of bringing acoarsely pulverized cellulose ether into contact with a cooledheat-transfer surface is preferably 10 seconds to 60 minutes, morepreferably 1 minute to 30 minutes. When the residence time is less than10 seconds, cooling may be insufficient so that a water-solublecellulose ether having a high loose bulk density may not be obtained.When the residence time is more than 60 minutes, an excessively largedevice may be needed.

In the method of bringing a coarsely pulverized cellulose ether intocontact with a cooled heat-transfer surface, static cooling or coolingwith stirring may be used; The cooling with stirring is preferred fromthe viewpoint of more efficient cooling.

The device to be used for the cooling with stirring may be a knowndevice. Examples thereof include a ribbon mixer, a screw mixer, a rotormixer with pins, a paddle mixer, a mixer with paddles, a proshear mixer,a twin-screw kneader, a co-kneader, a votator kneader, a self-cleaningkneader, and a biaxial kneader.

The stirring speed of the device to be used for the cooling withstirring is preferably 0.05 to 150 m/s, more preferably 0.1 to 20 m/s,even more preferably 0.2 to 10 m/s in terms of the peripheral speed of astirring propeller. When the stirring speed is less than 0.05 m/s,cooling may be inefficient. When the stirring speed is more than 150m/s, the power consumption for stirring may be excess, or water in astirring mixture may evaporate so that a water-soluble cellulose etherhaving a high loose bulk density may not be obtained.

The drying and the pulverization may be carried out separately orconcurrently. For example, the cooled coarsely pulverized celluloseether may be dried and then pulverized, or may be concurrently dried andpulverized. The temperature for drying and pulverization is preferably70 to 140° C. from the viewpoint of suppressing viscosity reduction orenergy consumption.

The temperature for drying and pulverization is higher than thetemperature at which the coarsely pulverized cellulose ether loses thefiber shape thereof so that it does not affect the fiber shape. Hence,strict control of the temperature for drying and pulverization is notnecessary to achieve a high loose bulk density.

Examples of the dryer may include a stirring dryer such as a paddledrier; a fluidized bed dryer; and a hand dryer. Examples of thepulverizer may include a ball mill, a vibration mill, an impact grinder,a roller mill, and a jet mill. Examples of the method of concurrentdrying and pulverization include a method of introducing a heated gastogether with the cooled coarsely pulverized cellulose ether into animpact grinder.

The water-soluble cellulose ether obtained after the drying andpulverization may be optionally sieved, and parts obtained by sievingmay be optionally combined.

Examples of the water-soluble cellulose ether include an alkylcellulose, a hydroxyalkyl cellulose, and a hydroxyalkyl alkyl cellulose.

Examples of the alkyl cellulose include methyl cellulose having a DS(degree of substitution) of methoxy group of 1.8 to 2.2 and ethylcellulose having a DS of ethoxy group of 2.0 to 2.6 from the viewpointof obtaining a water-soluble cellulose ether having the decreased numberof undissolved fibers.

Examples of the hydroxyalkyl cellulose include hydroxyethyl cellulosehaving an MS (molar substitution) of hydroxyethoxy group of 2.0 to 3.0and hydroxypropyl cellulose having an MS of hydroxypropoxy group of 2.0to 3.3 from the viewpoint of obtaining a water-soluble cellulose etherhaving the decreased number of undissolved fibers.

Examples of the hydroxyalkyl alkyl cellulose include hydroxyethyl methylcellulose having a DS of methoxy group of 1.3 to 2.2 and an MS ofhydroxyethoxy group of 0.1 to 0.6, hydroxypropyl methyl cellulose havinga DS of methoxy group of 1.3 to 2.2 and an MS of hydroxypropoxy group of0.1 to 0.6, and hydroxyethyl ethyl cellulose having a DS of ethoxy groupof 1.3 to 2.2 and an MS of hydroxyethoxy group of 0.1 to 0.6 from theviewpoint of obtaining a water-soluble cellulose ether having thedecreased number of undissolved fibers.

The DS means the degree of substitution and is the number of alkoxygroups per glucose ring unit of a cellulose. The MS means a molarsubstitution and is the average molar number of hydroxy alkoxy groupsadded to a glucose ring unit of a cellulose. The DS and the MS may bedetermined by converting values obtained by the measurement inaccordance with the Japanese Pharmacopoeia Seventeenth Edition.

The water-soluble cellulose ether preferably has an average particlesize of 30 to 300 μm, more preferably 40 to 200 μm, even more preferably50 to 100 μm from the viewpoint of flowability or dissolution rate. Theaverage particle size may be determined by the measurement with a laserdiffraction particle size distribution analyzer, MASTERSIZER 3000(manufactured by Malvern) by a dry method based on the Fraunhoferdiffraction theory in conditions of a dispersion pressure of 2 bar and ascattering intensity of 2 to 10%, wherein a diameter corresponding tothe 50% cumulative value on a volume-based cumulative distribution curveis selected as the average particle size.

The water-soluble cellulose ether preferably has a loose bulk density of0.36 to 0.60 g/ml, more preferably 0.37 to 0.55 g/ml. When the loosebulk density is less than 0.36 g/ml, a water-soluble cellulose ether mayhave poor powder flowability. When the loose bulk density is more than0.60 g/ml, a dissolution rate of a water-soluble cellulose ether inwater or others may be lowered. The “loose bulk density” is a bulkdensity in a loosely packed state and may be determined with a powdercharacteristic evaluation apparatus, POWDER TESTER PT-S, manufactured byHosokawa Micron Corporation, by the method comprising steps of:uniformly feeding a sample powder sieved through a sieve having a meshsize of 1 mm from 23 cm above into a cylindrical stainless steelcontainer having a diameter of 5.05 cm and a height of 5.05 cm (volume:100 ml); then leveling off the top surface of the container; andweighing the sample in the container.

A 2% by mass aqueous solution of the water-soluble cellulose etherpreferably has a viscosity at 20° C. of 30,000 to 500,000 mPa·s, morepreferably 50,000 to 300,000 mPa·s from the viewpoint of viscosity andsolubility suited for applications. The viscosity at 20° C. of 2% bymass aqueous solution of the water-soluble cellulose ether may bedetermined with a single cylinder-type rotational viscometer (Brookfieldtype viscometer type LV) in accordance with Method II of viscositymeasurement of hypromellose in the Japanese Pharmacopoeia SeventeenthEdition.

The number of undissolved fibers, each fiber having a dimension of 8 to200 μm, is preferably 800 or less, more preferably 750 or less in 2 mlof 0.1% by mass aqueous solution of the water-soluble cellulose ether at25° C. from the viewpoint of product qualities. The number ofundissolved fibers may be determined by a Coulter counter method with aCoulter counter or a Multisizer. More specifically, the number ofundissolved fibers is determined in the method comprising steps of:dissolving a water-soluble cellulose ether in an aqueous electrolytesolution for a Coulter counter, ISOTON II (manufactured by BeckmannCoulter Corporation) in a constant temperature bath of 25° C. in such anamount as to obtain a 0.1% by mass aqueous solution; and counting thenumber of undissolved fibers, each fiber having a dimension of 8 μm ormore and 200 μm or less present, in 2 ml of the solution by using anaperture tube having a diameter of 400 μm and a Coulter Counter TA II ora Multisizer manufactured by Coulter Corporation.

EXAMPLES

The present invention will next be described in detail with reference toExamples and Comparative Examples. It should not be construed that theinvention is limited by or to Examples.

Example 1

A pulp sheet having an intrinsic viscosity of 1,800 ml/g and a thicknessof 1.5 mm was immersed in a 49% by mass aqueous NaOH solution of 39° C.for 31 seconds. The mass ratio of the 49% by mass aqueous NaOH solutionin the alkali cellulose mixture to the solid component in pulp was 200.Then the pulp sheet was pressed to remove an excess 49% by mass aqueousNaOH solution to obtain alkali cellulose. The mass ratio of the NaOHcomponent in the alkali cellulose to the solid component in pulp was1.06.

Next, 17.9 kg of the alkali cellulose was placed in an internal-stirringpressure-resistant reactor with a jacket, and vacuumed and purged withnitrogen to thoroughly remove the oxygen in the reactor. Then, theinside of the reactor was stirred while adjusting the inside temperatureof the reactor to 60° C. Subsequently, 2.2 kg of dimethyl ether wasadded thereto, while the inside of the temperature was adjusted to 60°C. After the addition of dimethyl ether, while increasing the insidetemperature of the reactor from 60° C. to 80° C., methyl chloride wasadded in such an amount as to make a molar ratio of (methyl chloride) to(NaOH component in alkali cellulose) to be 1.3, and propylene oxide wasadded in such an amount as to make a mass ratio of (propylene oxide) to(solid component in pulp) to be 0.26. After the addition of methylchloride and propylene oxide, the inside temperature of the reactor wasincreased from 80° C. to 90° C., and the reaction was continued at 90°C. for another 20 minutes. The gas in the reactor was then discharged,and crude hydroxypropyl methyl cellulose was taken out of the reactor.

The crude hydroxypropyl methyl cellulose was dispersed in hot water of95° C., and then drained to obtain a first moist cellulose ether in ablock shape. The first moist cellulose ether had a temperature of 85° C.and a water content of 50% by mass.

While the first moist cellulose ether was stirred in a batch typeproshear mixer being equipped with a spray nozzle and having a jackettemperature of 90° C., water of 85° C. was continuously supplied fromthe spray nozzle over 5 minutes thereto in such an amount that a secondmoist cellulose ether had a water content of 80% by mass. The mixingwith stirring was continued for another 5 minutes to obtain a secondmoist cellulose ether. The second moist cellulose ether had atemperature of 85° C. and a water content of 80% by mass. The secondmoist cellulose ether had an average particle size of 15 mm, which wasseparately measured as the particle size at an integrated value of 50%in a mass-based cumulative particle size distribution as determined fromthe ratios of particles passing through five sieves having differentopenings (22.4 mm, 16.0 mm, 11.2 mm, 8.0 mm and 4.0 mm). Several gramsof sample were collected from each of five different positions in thesurface part or from each of five different positions in the center partof the second moist cellulose ether, and an average of the watercontents at the five positions was calculated. The absolute value of thedifference in (average) water content between the surface part to thecenter part was 3.5% by mass, and the water content ratio of the surfacepart to the center part was 1.05:1.00. Successively, the second moistcellulose ether was coarsely pulverized with a feather mill(manufactured by Hosokawa Micron Corporation) to obtain a coarselypulverized cellulose ether. The coarsely pulverized cellulose ether hada temperature of 60° C. and a water content of 78% by mass. Severalgrams of sample were collected from each of five different positions inthe surface part or from each of five different positions in the centerpart of the coarsely pulverized cellulose ether, and an average of thewater contents at the five positions was calculated. Subsequently, theabsolute value of the difference in (average) water content between thesurface part to the center part was calculated to be 0.5% by mass, andthe water content ratio of the surface part to the center part was1.01:1.00. The coarsely pulverized cellulose ether had an averageparticle size of 8 mm, which was separately measured as the particlesize at an integrated value of 50% in a mass-based cumulative particlesize distribution determined from the ratios of particles passingthrough five sieves having different openings (16.0 mm, 11.2 mm, 8.0 mm,4.0 mm and 2.0 mm).

The residence time in the pulverizer during the coarse pulverization wasabout 1 second, the pulverizing blade of the coarse pulverizer was aknife blade, and the circumferential speed thereof was 79 m/s.

The obtained coarsely pulverized cellulose ether was cooled to 15° C. bybeing mixed and granulated in a batch type proshear mixer having ajacket temperature of 5° C., and was then introduced into an Ultra RotorIIS impact mill (manufactured Altenburger Maschinen Jaeckering) whichwas driven at a pulverizing blade tip-circumferential speed of 108 m/sand was subjected to addition of a high temperature gas of 120° C.containing nitrogen at a speed of 800 m³/hr. Thus, the coarselypulverized cellulose ether was dried and pulverized concurrently toobtain a hydroxypropyl methyl cellulose powder.

The hydroxypropyl methyl cellulose powder had a degree of substitution(DS) of methoxy group of 1.80 and a molar substitution (MS) ofhydroxypropoxy group of 0.16. A viscosity at 20° C. of a 2% by massaqueous solution of the hydroxypropyl methyl cellulose powder was110,000 mPa·s. A loose bulk density of the hydroxypropyl methylcellulose powder was 0.48 g/mL as determined with a powdercharacteristic evaluation apparatus, POWDER TESTER PT-S, manufactured byHosokawa Micron Corporation. An average particle size of thehydroxypropyl methyl cellulose powder was 59 μm, which was determined asthe particle size at an integrated value of 50% on a volume-basedcumulative distribution curve obtained from the measurement by a laserdiffraction particle size distribution analyzer, MASTERSIZER 3000(manufactured by Malvern) using a dry method. The number of undissolvedfibers, each fiber having a dimension of 8 to 200 μm, was 720, which wasdetermined at 25° C. in 2 ml of a 0.1% by mass aqueous solution of thehydroxypropyl methyl cellulose powder by using a Multisizer 3(manufactured by Beckmann Coulter Corporation). The results aresummarized in Tables 1 and 2 below.

Example 2

A first moist cellulose ether in a block shape was obtained in the samemanner as in Example 1. The first moist cellulose ether had atemperature of 85° C. and a water content of 45% by mass.

A second moist cellulose ether was obtained from the first moistcellulose ether in the same manner as in Example 1 except that water wassupplied in such an amount that the second moist cellulose ether had awater content of 75% by mass. The second moist cellulose ether had atemperature of 85° C. and a water content of 75% by mass. The averageparticle size was 16 mm, which was determined in the same manner as inExample 1.

In the second moist cellulose ether, the absolute value of thedifference in water content between the surface part and the center partwas 3.8% by mass, and the water content ratio of the surface part to thecenter part was 1.05:1.00, which were determined in the same manner asin Example 1.

Subsequently, the second moist cellulose ether was coarsely pulverizedin the same manner as in Example 1 to obtain a coarsely pulverizedcellulose ether. The coarsely pulverized cellulose ether had atemperature of 60° C. and a water content of 73% by mass. The averageparticle size was 8 mm, which was determined in the same manner as inExample 1. In the coarsely pulverized cellulose ether, the absolutevalue of the difference in water content between the surface part andthe center part was 0.8% by mass, and the water content ratio of thesurface part to the center part was 1.01:1.00, which were determined inthe same manner as in Example 1.

The coarsely pulverized cellulose ether was cooled to 15° C. in the samemanner as in Example 1, and then was dried and pulverized concurrentlyto obtain a hydroxypropyl methyl cellulose powder. The hydroxypropylmethyl cellulose powder had a degree of substitution (DS) of methoxygroup of 1.80 and a molar substitution (MS) of hydroxypropoxy group of0.16. A viscosity at 20° C. of a 2% by mass aqueous solution of thehydroxypropyl methyl cellulose powder was 103,000 mPa·s. A loose bulkdensity of the hydroxypropyl methyl cellulose powder was 0.46 g/mL, avolume-based average particle size thereof was 62 μm by dry laserdiffractometry, and the number of undissolved fibers, each fiber havinga dimension of 8 to 200 μm, was 680 at 25° C. in 2 ml of a 0.1% by massaqueous solution thereof, which were determined in the same manner as inExample 1. The results are summarized in Tables 1 and 2 below.

Example 3

A pulp sheet having an intrinsic viscosity of 2,000 ml/g and a thicknessof 1.2 mm was immersed in a 49% by mass aqueous NaOH solution of 39° C.for 40 seconds. The mass ratio of the 49% by mass aqueous NaOH solutionin the alkali cellulose mixture to the solid component in pulp was 200.Then, the pulp sheet was pressed to remove an excess 49% by mass aqueousNaOH solution to obtain alkali cellulose. The mass ratio of the NaOHcomponent in the alkali cellulose to the solid component in pulp was1.25.

Next, 20.0 kg of the alkali cellulose was placed in an internal-stirringpressure-resistant reactor with a jacket, and vacuumed and purged withnitrogen to thoroughly remove the oxygen in the reactor. The inside ofthe reactor was stirred, while the inside temperature of the reactor wasadjusted to 60° C. Subsequently, 2.2 kg of dimethyl ether was added,while the inside temperature of the reactor was adjusted to 60° C. Afterthe addition of dimethyl ether, while increasing the inside temperatureof the reactor from 60° C. to 80° C., methyl chloride was added in suchan amount as to make a molar ratio of (methyl chloride) to (NaOHcomponent in alkali cellulose) to be 1.3, and propylene oxide was addedin such an amount to make a mass ratio of (propylene oxide) to (solidcomponent in pulp) to be 0.52. After the addition of methyl chloride andpropylene oxide, the inside temperature of the reactor was increasedfrom 80° C. to 90° C., and the reaction was continued at 90° C. foranother 20 minutes. The gas in the reactor was then discharged, and acrude hydroxypropyl methyl cellulose was taken out of the reactor.

A first moist cellulose ether in a block shape was obtained from thecrude hydroxypropyl methyl cellulose in the same manner as in Example 1.The first moist cellulose ether had a temperature of 85° C. and a watercontent of 49% by mass.

A second moist cellulose ether was obtained from the first moistcellulose ether in the same manner as in Example 1 except that thejacket temperature was 80° C. and water was supplied in such an amountthat the second moist cellulose ether had a water content of 65% bymass. The second moist cellulose ether had a temperature of 75° C. and awater content of 65% by mass. The average particle size was 16 mm, whichwas determined in the same manner as in Example 1.

In the second moist cellulose ether, the absolute value of thedifference in water content between the surface part and the center partwas 2.8% by mass, and the water content ratio of the surface part to thecenter part was 1.05:1.00, which were determined in the same manner asin Example 1.

Subsequently, the second moist cellulose ether was coarsely pulverizedin the same manner as in Example 1 to obtain a coarsely pulverizedcellulose ether. The coarsely pulverized cellulose ether had atemperature of 55° C. and a water content of 64% by mass. The averageparticle size was 7 mm, which was determined in the same manner as inExample 1. In the coarsely pulverized cellulose ether, the absolutevalue of the difference in water content between the surface part andthe center part was 0.5% by mass, and the water content ratio of thesurface part to the center part was 1.01:1.00, which were determined inthe same manner as in Example 1.

The coarsely pulverized cellulose ether was cooled to 15° C. in the samemanner as in Example 1 and then was dried and pulverized concurrently toobtain a hydroxypropyl methyl cellulose powder. The hydroxypropyl methylcellulose powder had a degree of substitution (DS) of methoxy group of1.90 and a molar substitution (MS) of hydroxypropoxy group of 0.24. Aviscosity at 20° C. of a 2% by mass aqueous solution of thehydroxypropyl methyl cellulose powder was 110,000 mPa·s. A loose bulkdensity of the hydroxypropyl methyl cellulose powder was 0.43 g/mL, avolume-based average particle size thereof was 65 μm by dry laserdiffractometry, and the number of undissolved fibers, each fiber havinga dimension of 8 to 200 μm, was 260 at 25° C. in 2 ml of a 0.1% by massaqueous solution thereof. The results are summarized in Tables 1 and 2below.

Example 4

A first moist cellulose ether in a block shape was obtained in the samemanner as in Example 1. The first moist cellulose ether had atemperature of 85° C. and a water content of 45% by mass.

The first moist cellulose ether was supplied at 10 kg/hr to a screwconveyor held at 80° C., and concurrently hot water of 95° C. was addedat 8.33 kg/hr from an inlet of the screw conveyor-type conveyor, therebyobtaining a second moist cellulose ether in a block shape and beingdischarged from an outlet of the screw conveyor. The second moistcellulose ether had a temperature of 80° C. and a water content of 70%by mass. The second moist cellulose ether in a block shape was loosenedby hands. In the loosened second moist cellulose ether, the absolutevalue of the difference in water content between the surface part andthe center part was 3.6% by mass, and the water content ratio of thesurface part to the center part was 1.05:1.00, which were determined inthe same manner as in Example 1.

Subsequently, the second moist cellulose ether was coarsely pulverizedin the same manner as in Example 1 to obtain a coarsely pulverizedcellulose ether. The coarsely pulverized cellulose ether had atemperature of 60° C. and a water content of 69% by mass. The averageparticle size was 7 mm, which was determined in the same manner as inExample 1. In the coarsely pulverized cellulose ether, the absolutevalue of the difference in water content between the surface part andthe center part was 0.6% by mass, and the water content ratio of thesurface part to the center part was 1.01:1.00, which were determined inthe same manner as in Example 1.

The coarsely pulverized cellulose ether was cooled to 15° C. in the samemanner as in Example 1, and then was dried and pulverized concurrentlyto obtain a hydroxypropyl methyl cellulose powder. The hydroxypropylmethyl cellulose powder had a degree of substitution (DS) of methoxygroups of 1.80 and a molar substitution (MS) of hydroxypropoxy groups of0.16. A viscosity at 20° C. of a 2% by mass aqueous solution of thehydroxypropyl methyl cellulose powder was 106,000 mPa·s. A loose bulkdensity of The hydroxypropyl methyl cellulose powder was 0.41 g/mL, avolume-based average particle size thereof was 63 μm by dry laserdiffractometry, and the number of undissolved fibers, each fiber havinga dimension of 8 to 200 μm, was 550 at 25° C. in 2 ml of a 0.1% by massaqueous solution thereof. The results are summarized in Tables 1 and 2below.

Example 5

A first moist cellulose ether in a block shape was obtained in the samemanner as in Example 1. The first moist cellulose ether had atemperature of 85° C. and a water content of 45% by mass.

A second moist cellulose ether in a block shape was obtained from thefirst moist cellulose ether in the same manner as in Example 4 exceptthat hot water of 95° C. was supplied at 5.71 kg/hr. The second moistcellulose ether had a temperature of 75° C. and a water content of 65%by mass. The second moist cellulose ether in a block shape was loosenedby hands. In the loosened second moist cellulose ether, the absolutevalue of the difference in water content between the surface part andthe center part was 3.5% by mass, and the water content ratio of thesurface part to the center part was 1.06:1.00, which were determined inthe same manner as in Example 1.

Subsequently, the second moist cellulose ether was coarsely pulverizedin the same manner as in Example 1 to obtain a coarsely pulverizedcellulose ether. The coarsely pulverized cellulose ether had atemperature of 50° C. and a water content of 64% by mass. The averageparticle size was 8 mm, which was determined in the same manner as inExample 1. In the coarsely pulverized cellulose ether, the absolutevalue of the difference in water content between the surface part andthe center part was 0.7% by mass, and the water content ratio of thesurface part to the center part was 1.01:1.00, which were determined inthe same manner as in Example 1.

The coarsely pulverized cellulose ether was cooled to 15° C. in the samemanner as in Example 1, and then was dried and pulverized concurrentlyto obtain a hydroxypropyl methyl cellulose powder. The hydroxypropylmethyl cellulose powder had a degree of substitution (DS) of methoxygroup of 1.80 and a molar substitution (MS) of hydroxypropoxy group of0.16. A viscosity at 20° C. of a 2% by mass aqueous solution of thehydroxypropyl methyl cellulose powder was 110,000 mPa·s. A loose bulkdensity of the hydroxypropyl methyl cellulose powder was 0.37 g/mL, avolume-based average particle size thereof was 63 μm by dry laserdiffractometry, and the number of undissolved fibers, each fiber havinga dimension of 8 to 200 μm, was 500 at 25° C. in 2 ml of a 0.1% by massaqueous solution thereof. The results are summarized in Tables 1 and 2below.

Example 6

A first moist cellulose ether in a block shape was obtained in the samemanner as in Example 3. The first moist cellulose ether had atemperature of 85° C. and a water content of 48% by mass.

A second moist cellulose ether in a block shape was obtained from thefirst moist cellulose ether in the same manner as in Example 4 exceptthat hot water of 95° C. was supplied at 5.41 kg/hr. The second moistcellulose ether had a temperature of 75° C. and a water content of 65%by mass.

The second moist cellulose ether in a block shape was loosened by hands.In the loosened second moist cellulose ether, the absolute value of thedifference in water content between the surface part and the center partwas 4.0% by mass, and the water content ratio of the surface part to thecenter part was 1.07:1.00, which were determined in the same manner asin Example 1.

Subsequently, the second moist cellulose ether was coarsely pulverizedin the same manner as in Example 1 to obtain a coarsely pulverizedcellulose ether. The coarsely pulverized cellulose ether had atemperature of 55° C. and a water content of 64% by mass. The averageparticle size was 7 mm, which was determined in the same manner as inExample 1. In the coarsely pulverized cellulose ether, the absolutevalue of the difference in water content between the surface part andthe center part was 0.6% by mass, and the water content ratio of thesurface part to the center part was 1.01:1.00, which were determined inthe same manner as in Example 1.

The coarsely pulverized cellulose ether was cooled to 15° C. in the samemanner as in Example 1, then was dried with an air dryer set at 80° C.for 8 hours, and was pulverized with a vibration mill, CH-20(manufactured by Chuo Kakohki Co., Ltd.). The pulverized product wassieved with a Gyro-Sifter GS-A1H (manufactured by TOKUJU CORPORATION) toremove coarse cellulose ether, thereby obtaining a hydroxypropyl methylcellulose powder. The hydroxypropyl methyl cellulose powder had a degreeof substitution (DS) of methoxy group of 1.90 and a molar substitution(MS) of hydroxypropoxy group of 0.24. A viscosity at 20° C. of a 2% bymass aqueous solution of the hydroxypropyl methyl cellulose powder was83,000 mPa·s. A loose bulk density of the hydroxypropyl methyl cellulosepowder was 0.38 g/mL, a volume-based average particle size thereof was70 μm by dry laser diffractometry, and the number of undissolved fibers,each fiber having a dimension of 8 to 200 μm, was 320 at 25° C. in 2 mlof a 0.1% by mass aqueous solution thereof. The results are summarizedin Tables 1 and 2 below.

Example 7

A pulp sheet having an intrinsic viscosity of 1,900 ml/g and a thicknessof 1.2 mm was made into 15-mm-square chips. The pulp chips were immersedin a 49% by mass aqueous NaOH solution of 32° C. for 34 seconds. Themass ratio of 49% by mass aqueous NaOH solution in the alkali cellulosemixture to the solid component in pulp was 15. Then, the pulp sheet waspressed by using a rotary basket having a centrifugal effect of 600 toremove an excess 49% by mass aqueous NaOH solution, thereby obtainingalkali cellulose. The mass ratio of NaOH component in the alkalicellulose to the solid component in pulp was 1.059. A crudehydroxypropyl methyl cellulose was obtained from the alkali cellulose asthe raw material in the same manner as in Example 1.

The crude hydroxypropyl methyl cellulose was dispersed in hot water inthe same manner as in Example 1 and then was drained to obtain a firstmoist cellulose ether in a block shape. The first moist cellulose etherhad a temperature of 85° C. and a water content of 48% by mass.

A second moist cellulose ether in a block shape was obtained from thefirst moist cellulose ether in the same manner as in Example 4 exceptthat hot water of 95° C. was supplied at 8.03 kg/hr. The second moistcellulose ether had a temperature of 80° C. and a water content of 70%by mass.

The second moist cellulose ether in a block shape was loosened by hands.In the loosened second moist cellulose ether, the absolute value of thedifference in water content between the surface part and the center partwas 4.8% by mass, and the water content ratio of the surface part to thecenter part was 1.07:1.00, which were determined in the same manner asin Example 1.

Subsequently, the second moist cellulose ether was coarsely pulverizedin the same manner as in Example 1 to obtain a coarsely pulverizedcellulose ether. The coarsely pulverized cellulose ether had atemperature of 60° C. and a water content of 69% by mass. The averageparticle size was 7 mm, which was determined in the same manner as inExample 1. In the coarsely pulverized cellulose ether, the absolutevalue of the difference in water content between the surface part andthe center part was 0.6% by mass, and the water content ratio of thesurface part to the center part was 1.01:1.00, which were determined inthe same manner as in Example 1.

The coarsely pulverized cellulose ether was cooled to 15° C. in the samemanner as in Example 1 and was subjected to the same procedure as inExample 6 to obtain a hydroxypropyl methyl cellulose powder. Thehydroxypropyl methyl cellulose powder had a degree of substitution (DS)of methoxy group of 1.80 and a molar substitution (MS) of hydroxypropoxygroup of 0.16. A viscosity at 20° C. of a 2% by mass aqueous solution ofthe hydroxypropyl methyl cellulose powder was 83,000 mPa·s. A loose bulkdensity of the hydroxypropyl methyl cellulose powder was 0.37 g/mL, avolume-based average particle size thereof was 65 μm by dry laserdiffractometry, and the number of undissolved fibers, each fiber havinga dimension of 8 to 200 μm, was 680 at 25° C. in 2 ml of a 0.1% by massaqueous solution thereof. The results are summarized in Tables 1 and 2below.

Comparative Example 1

A first moist cellulose ether in a block shape was obtained in the samemanner as in Example 1. The first moist cellulose ether had atemperature of 85° C. and a water content of 46% by mass.

In the same manner as in Example 1, the first moist cellulose ether wasgranulated with stirring in a proshear mixer, being equipped with aspray nozzle and having a jacket temperature of 60° C., while water of60° C. was continuously supplied thereto through the spray nozzle over 5minutes in such an amount that a second moist cellulose ether had awater content of 70% by mass. After the water was supplied, mixing withstirring was continued for 20 minutes to obtain the second moistcellulose ether. The second moist cellulose ether had a temperature of60° C. and a water content of 70% by mass. The second moist celluloseether had an average particle size of 10 mm, which was separatelymeasured as the particle size at an integrated value of 50% in amass-based cumulative particle size distribution determined from ratiosof particles passing through five sieves having different openings (16.0mm, 11.2 mm, 8.0 mm, 4.0 mm and 2.0 mm). In the second moist celluloseether, the absolute value of the difference in water content between thesurface part and the center part was 4.5% by mass, and the water contentratio of the surface part to the center part was 1.07:1.00, which weredetermined in the same manner as in Example 1. It was confirmed that thepenetration of water into the center part had been insufficient.

The second moist cellulose ether was not subjected to the coarsepulverization, and was dried and pulverized concurrently in the samemanner as in Example 1 to obtain a hydroxypropyl methyl cellulosepowder. The hydroxypropyl methyl cellulose powder had a degree ofsubstitution (DS) of methoxy group of 1.80 and a molar substitution (MS)of hydroxypropoxy group of 0.16. A viscosity at 20° C. of a 2% by massaqueous solution of the hydroxypropyl methyl cellulose powder was100,000 mPa·s. A low loose bulk density of the hydroxypropyl methylcellulose powder was 0.10 g/mL, a volume-based average particle sizethereof was 150 μm by dry laser diffractometry, and the number ofundissolved fibers, each fiber having a dimension of 8 to 200 μm, was aslarge as 1,100 at 25° C. in 2 ml of a 0.1% by mass aqueous solutionthereof. The results are summarized in Tables 1 and 2 below.

Comparative Example 2

A first moist cellulose ether in a block shape was obtained in the samemanner as in Example 1. The first moist cellulose ether had atemperature of 85° C. and a water content of 45% by mass.

The first moist cellulose ether was supplied at 10 kg/hr to a screwconveyor held at 80° C., and concurrently hot water of 95° C. was addedat 8.33 kg/hr from an inlet of the screw conveyor, thereby obtaining asecond moist cellulose ether in a block shape and being discharged froman outlet of the screw conveyor. The second moist cellulose ether had atemperature of 80° C. and a water content of 70% by mass. In the secondmoist cellulose ether, the absolute value of the difference in watercontent between the surface part and the center part was 3.2% by mass,and the water content ratio of the surface part to the center part was1.05:1.00, which were determined in the same manner as in Example 1. Itwas confirmed that the penetration of water into the center part hadbeen insufficient.

The second moist cellulose ether was not subjected to the coarsepulverization and was cooled in the same manner as in Example 1, andthen dried and pulverized concurrently to obtain a hydroxypropyl methylcellulose powder. The hydroxypropyl methyl cellulose powder had a degreeof substitution (DS) of methoxy group of 1.80 and a molar substitution(MS) of hydroxypropoxy group of 0.16. A viscosity at 20° C. of a 2% bymass aqueous solution of the hydroxypropyl methyl cellulose powder was100,000 mPa·s. A loose bulk density of the hydroxypropyl methylcellulose powder was as small as 0.21 g/mL, a volume-based averageparticle size thereof was 80 μm by dry laser diffractometry, and thenumber of undissolved fibers, each fiber having a dimension of 8 to 200μm, was as many as 900 at 25° C. in 2 ml of a 0.1% by mass aqueoussolution thereof. The results are summarized in Tables 1 and 2 below.

TABLE 1 second moisture cellulose ether first moisture average celluloseether particle form of water water size by cellulose temp. content temp.content sieving pulp (° C.) (%) form (° C.) (%) apparatus*1 form (mm)Example1 sheet 85 50 block 85 80 P — 15 Example2 sheet 85 45 block 85 75P — 16 Example3 sheet 85 49 block 75 65 P — 16 Example4 sheet 85 45block 80 70 SC block — Example5 sheet 85 45 block 75 65 SC block —Example6 sheet 85 48 block 75 65 SC block — Example7 chips 85 48 block80 70 SC block — Comp. Ex. 1 sheet 85 46 block 60 70 P — 10 Comp. Ex. 2sheet 85 45 block 80 70 SC block — coarsely pulverized cellulose etheraverage particle temp. use of water size by after drying and coarsetemp. content sieving cooling pulverization pulverizer (° C.) (%) (mm)(° C.) — Example1 used 60 78 8 15 concurrent Example2 use 60 73 8 15concurrent Example3 used 55 64 7 15 concurrent Example4 used 60 69 7 15concurrent Example5 used 50 64 8 15 concurrent Example6 used 55 64 7 15drying followed by pulverization Example7 used 60 69 7 15 dryingfollowed by pulverization Comp. Ex. 1 not used — — — — concurrent Comp.Ex. 2 not used — — — — concurrent *1“P” means a proshear mixer equippedwith a spray nozzle and “SC” means a screw conveyer mixer.

TABLE 2 water-soluble cellulose ether volume-based viscosity average at20° C. number of particle loose bulk of 2% by mass undissolved sizedensity aq. solution fibers DS MS (μm) (g/ml) (mPa · s) (pieces)Example1 1.80 0.16 59 0.48 110000 720 Example2 1.80 0.16 62 0.46 103000680 Example3 1.90 0.24 65 0.43 110000 260 Example4 1.80 0.16 63 0.41106000 550 Example5 1.80 0.16 63 0.37 110000 500 Example6 1.90 0.24 700.38 83000 320 Example7 1.80 0.16 65 0.37 83000 680 Comp. Ex. 1 1.800.16 150 0.10 100000 1100 Comp. Ex. 2 1.80 0.16 80 0.21 100000 900

1. A water-soluble cellulose ether, having a loose bulk density of 0.36to 0.60 g/ml and a viscosity at 20° C. of 30,000 to 500,000 mPa·s asdetermined in a 2% by mass aqueous solution of the water-solublecellulose ether, and containing 800 or less of undissolved fibers, eachfiber having a dimension of 8 to 200 μm, as determined by a Coultercounter method at 25° C. in 2 ml of a 0.1% by mass aqueous solution ofthe water-soluble cellulose ether.
 2. The water-soluble cellulose etheraccording to claim 1, further having an average particle size of 30 to300 μm.
 3. The water-soluble cellulose ether according to claim 1,wherein the water-soluble cellulose ether is an alkyl cellulose, ahydroxyalkyl cellulose, or a hydroxyalkyl alkyl cellulose.
 4. Thewater-soluble cellulose ether according to claim 1, wherein thewater-soluble cellulose ether is an alkyl cellulose selected from thegroup consisting of methyl cellulose having a degree of substitution(DS) of methoxy group of 1.8 to 2.2 and ethyl cellulose having a DS ofethoxy group of 2.0 to 2.6.
 5. The water-soluble cellulose etheraccording to claim 1, wherein the water-soluble cellulose ether is ahydroxyalkyl cellulose selected from the group consisting ofhydroxyethyl cellulose having a molar substitution (MS) of hydroxyethoxygroup of 2.0 to 3.0 and hydroxypropyl cellulose having an MS ofhydroxypropoxy group of 2.0 to 3.3.
 6. The water-soluble cellulose etheraccording to claim 1, wherein the water-soluble cellulose ether is ahydroxyalkyl alkyl cellulose selected from the group consisting ofhydroxyethyl methyl cellulose having a DS of methoxy group of 1.3 to 2.2and an MS of hydroxyethoxy group of 0.1 to 0.6, hydroxypropyl methylcellulose having a DS of methoxy group of 1.3 to 2.2 and an MS ofhydroxypropoxy group of 0.1 to 0.6, and hydroxyethyl ethyl cellulosehaving a DS of ethoxy group of 1.3 to 2.2 and an MS of hydroxyethoxygroup of 0.1 to 0.6.